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Ion-paired chiral ligands for asymmetric palladium catalysis

Nature Chemistry volume 4, pages 473–477 (2012)Cite this article

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Abstract

Conventional chiral ligands rely on the use of a covalently constructed, single chiral molecule embedded with coordinative functional groups. Here, we report a new strategy for the design of a chiral ligand for asymmetric transition-metal catalysis; our approach is based on the development of an achiral cationic ammonium–phosphine hybrid ligand paired with a chiral binaphtholate anion. This ion-paired chiral ligand imparts a remarkable stereocontrolling ability to its palladium complex, which catalyses a highly enantioselective allylic alkylation of α-nitrocarboxylates. By exploiting the possible combinations of the achiral onium entities with suitable coordinative functionalities and readily available chiral acids, this approach should contribute to the development of a broad range of metal-catalysed, stereoselective chemical transformations.

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Figure 1: Strategies for construction of a chiral environment around a metal catalyst.
Figure 2: ORTEP diagram of 3b.
Figure 3: Proposed catalytic cycle for enantioselective alkylation catalysed by an ion-paired chiral catalyst.
Figure 4: Derivatization of alkylation product 6a.

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References

  1. Jacobsen, E. N., Pfaltz, A. & Yamamoto, H. (eds) Comprehensive Asymmetric Catalysis, and Supplements 1 and 2 (Springer, 1999, 2004).

    Google Scholar 

  2. Yoon, T. P. & Jacobsen, E. N. Privileged chiral catalysts. Science 299, 1691–1693 (2003).

    Article  CAS  Google Scholar 

  3. Wiester, M. J., Ulmann, P. A. & Mirkin, C. A. Enzyme mimics based upon supramolecular coordination chemistry. Angew. Chem. Int. Ed. 50, 114–137 (2011).

    Article  CAS  Google Scholar 

  4. Breit, B. Catalysts through self-assembly for combinatorial homogeneous catalysis. Pure Appl. Chem. 80, 855–860 (2008).

    Article  CAS  Google Scholar 

  5. Meeuwissen, J. & Reek, J. N. H. Supramolecular catalysis beyond enzyme mimics. Nature Chem. 2, 615–621 (2010).

    Article  CAS  Google Scholar 

  6. Dydio, P., Rubay, C., Gadzikwa, T., Lutz, M. & Reek, J. N. H. ‘Cofactor’-controlled enantioselective catalysis. J. Am. Chem. Soc. 133, 17176–17179 (2011).

    Article  CAS  Google Scholar 

  7. van Leeuwen, P. W. N. M., Rivillo, D., Raynal, M. & Freixa, Z. Enantioselective supramolecular catalysis induced by remote chiral diols. J. Am. Chem. Soc. 133, 18562–18565 (2011).

    Article  CAS  Google Scholar 

  8. Hamilton, G. L., Kang, E. J., Mba, M. & Toste, F. D. A powerful chiral counterion strategy for asymmetric transition metal catalysis. Science 317, 496–499 (2007).

    Article  CAS  Google Scholar 

  9. Mukherjee, S. & List, B. Chiral counteranions in asymmetric transition-metal catalysis: highly enantioselective Pd/Brønsted acid-catalyzed direct α-allylation of aldehydes. J. Am. Chem. Soc. 129, 11336–11337 (2007).

    Article  CAS  Google Scholar 

  10. Liao, S. & List, B. Asymmetric counteranion-directed transition-metal catalysis: enantioselective epoxidation of alkenes with manganese(III) salen phosphate complexes. Angew. Chem. Int. Ed. 49, 628–631 (2010).

    Article  CAS  Google Scholar 

  11. Jiang, G. & List, B. Direct asymmetric α-allylation of aldehydes with simple allylic alcohols enabled by the concerted action of three different catalysts. Angew. Chem. Int. Ed. 50, 9471–9474 (2011).

    Article  CAS  Google Scholar 

  12. Jiang, G., Halder, R., Fang, Y. & List, B. A highly enantioselective Overman rearrangement through asymmetric counteranion-directed palladium catalysis. Angew. Chem. Int. Ed. 50, 9752–9755 (2011).

    Article  CAS  Google Scholar 

  13. Okano, T., Harada, N. & Kiji, J. Transition metal phosphine complexes possessing phase transfer function. Preparation and reactivities of palladium complexes containing quaternary ammonium groups. Chem. Lett. 23, 1057–1060 (1994).

    Article  Google Scholar 

  14. Chisholm, D. M. & McIndoe, J. S. Charged ligands for catalyst immobilisation and analysis. Dalton Trans. 3933–3945 (2008).

  15. Yuan, H., Zhou, Z., Xiao, J., Liang, L. & Dai, L. Preparation of quarternary ammonium salt-tagged ferrocenylphosphine–imine ligands and their application to palladium-catalyzed asymmetric allylic substitution. Tetrahedron: Asymmetry 21, 1874–1884 (2010).

    Article  CAS  Google Scholar 

  16. Sawamura, M., Nakayama, Y., Tang, W.-M. & Ito, Y. Enantioselective allylation of nitro group-stabilized carbanions catalyzed by chiral crown ether phosphine–palladium complexes. J. Org. Chem. 61, 9090–9096 (1996).

    Article  CAS  Google Scholar 

  17. Shipchandler, M. T. The utility of nitroacetic acid and its esters in organic synthesis. Synthesis 666–686 (1979).

    Article  Google Scholar 

  18. Trost, B. M. & Van Vranken, D. L. Asymmetric transition metal-catalyzed allylic alkylations. Chem. Rev. 96, 395–422 (1996).

    Article  CAS  Google Scholar 

  19. Trost, B. M. & Crawley, M. L. Asymmetric transition-metal-catalyzed allylic alkylations: applications in total synthesis. Chem. Rev. 103, 2921–2943 (2003).

    Article  CAS  Google Scholar 

  20. Mohr, J. T. & Stoltz, B. M. Enantioselective Tsuji allylations. Chem. Asian J. 2, 1476–1491 (2007).

    Article  CAS  Google Scholar 

  21. Lu, Z. & Ma, S. Metal-catalyzed enantioselective allylation in asymmetric synthesis. Angew. Chem. Int. Ed. 47, 258–297 (2008).

    Article  CAS  Google Scholar 

  22. Nakoji, M., Kanayama, T., Okino, T. & Takemoto, Y. Chiral phosphine-free Pd-mediated asymmetric allylation of prochiral enolate with a chiral phase-transfer catalyst. Org. Lett. 3, 3329–3331 (2001).

    Article  CAS  Google Scholar 

  23. Cativiela, C. & Díaz-de-Villegas, M. D. Recent progress on the stereoselective synthesis of acyclic quaternary α-amino acids. Tetrahedron: Asymmetry 18, 569–623 (2007).

    Article  CAS  Google Scholar 

  24. Amatore, C. & Jutand, A. Role of dba in the reactivity of palladium(0) complexes generated in situ from mixtures of Pd(dba)2 and phosphines. Coord. Chem. Rev. 178–180, 511–528 (1998).

    Article  Google Scholar 

  25. Guillaneux, D., Zhao, S.-H., Samuel, O., Rainford, D. & Kagan, H. B. Nonlinear effects in asymmetric catalysis. J. Am. Chem. Soc. 116, 9430–9439 (1994).

    Article  CAS  Google Scholar 

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Acknowledgements

Financial support was provided by the Funding Program for Next Generation World-Leading Researchers from JSPS (GR050) and the Global COE Program in Chemistry of Nagoya University.

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Authors and Affiliations

  1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, 464-8603, Japan

    Kohsuke Ohmatsu, Mitsunori Ito, Tomoatsu Kunieda & Takashi Ooi

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  1. Kohsuke Ohmatsu
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  2. Mitsunori Ito
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  3. Tomoatsu Kunieda
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  4. Takashi Ooi
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Contributions

K.O. and T.O. conceived and designed the study, and co-wrote the paper. K.O., M.I. and T.K. performed the experiments and analysed the data. All authors discussed the results and commented on the manuscript.

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Correspondence to Takashi Ooi.

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The authors declare no competing financial interests.

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Crystallographic data for compound 3b. (CIF 23 kb)

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Ohmatsu, K., Ito, M., Kunieda, T. et al. Ion-paired chiral ligands for asymmetric palladium catalysis. Nature Chem 4, 473–477 (2012). https://doi.org/10.1038/nchem.1311

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